Carbon Dioxide → (+)-2-Cyano-2-methylhexanol

HRID 2253717Notes

Reaction equation

HRID 2253717 reaction equation
C1CC[CH:4]([N:7]=C=NC2CCCCC2)CC1.[CH2:16]([O:23][C:24]1[CH:29]=[CH:28][C:27]([C:30]2[C:31]([F:40])([C:37]([OH:39])=O)[CH:32]([F:36])[CH:33]=[CH:34][CH:35]=2)=[CH:26][CH:25]=1)[CH2:17][CH2:18][CH2:19][CH2:20][CH2:21][CH3:22].FC1C(F)=CC=CC=1C1C=CC(OCCCCCCC)=CC=1.CN(CCN(C)C)C.[Li]CCCC.[C:76](=[O:78])=[O:77]>C(Cl)Cl.C1COCC1.CCCCCC>[CH2:16]([O:23][C:24]1[CH:25]=[CH:26][C:27]([C:30]2[CH:35]=[CH:34][C:33]([C:76]([OH:78])=[O:77])=[C:32]([F:36])[C:31]=2[F:40])=[CH:28][CH:29]=1)[CH2:17][CH2:18][CH2:19][CH2:20][CH2:21][CH3:22].[C:4]([C:31]([CH3:30])([CH2:32][CH2:33][CH2:34][CH3:35])[CH2:37][OH:39])#[N:7]

Participants

11

Reactant 6

HCID 280Carbon DioxideHCID 8037N,N,N',N'-TetramethylethylenediamineHCID 10868DicyclohexylcarbodiimideHCID 191036002,3-Difluoro-4'-heptyloxybiphenylHCID 678436304'-Heptyloxy-2,3-difluorobiphenylcarboxylic acidHCID 178418339Butyllithium

Product 2

HCID 14793448(+)-2-Cyano-2-methylhexanolHCID 191035324'-Heptyloxy-2,3-difluoro-biphenyl-4-carboxylic acid

Reagents, catalysts & solvents 3

HCID 6344DichloromethaneSolventHCID 8028TetrahydrofuranSolventHCID 8058HexaneSolvent

Conditions

Temperature
-78 °C

Procedure

At 0° C., 0.1 mol of DCC, dissolved in methylene chloride, is added to a mixture of 0.1 mol of 4'-heptyloxy-2,3-difluorobiphenylcarboxylic acid (preparation: 0.1 mol of 2,3-difluoro-4'-heptyloxybiphenyl and 0.1 mol of TMEDA are dissolved in 200 ml of THF, and the solution is cooled to -78° C. and reacted at this temperature with 0.105 mol of a 1.6N solution of BuLi in hexane. The reaction mixture is stirred at -78° C. for 3 hours and then tipped in one portion onto 200 g of powdered dry ice. After customary work-up, 4'-heptyloxy-2,3-difluorobiphenyl-4-carboxylic acid is obtained), 0.1 mol of optically active 2-cyano-2-methylhexan-1-ol (which can be prepared from optically active ethyl 2-methyl-2-butylcyanoacetate by reduction using LiBH4) and a catalytic amount of 4-N,N'-dimethylaminopyridine (DMAP) in 200 ml of methylene chloride. The mixture is subsequently stirred at room temperature for 12 hours and worked up in a customary manner, and the product is purified by crystallization, to give optically active 2-cyano-2-methylhexyl 4'-heptyloxy-2,3-difluorobiphenyl-4-carboxylate.

Workup

  1. custompreparation

Sources & evidence

ORD record
ord-d97545f17c4944a2862dcc906c4c7b78
Source dataset
uspto-grants-1993_08
Patent number
US05232624

Reaction notes

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